This invention pertains to the preparation of substituted olefins and more particularly to the reaction of organic halides with olefins in the presence of a zinc-triarylphosphine-nickel salt catalyst.
The quest for substituted olefins is a continuing one because of the use of such compounds as monomers to produce homopolymers and copolymers. Styrene is a typical example of such a compound. The activity of the vinyl group also provides a host of versatile intermediates for further reactions including but not limited to halogenation, hydrogenation, nitration, sulfonation, cyanoalkylation, amination, and the like.
The general reaction of an organic iodide or bromide with an olefin is well established with palladium catalysts as demonstrated in the publications listed below.
J. E. Plevyak and R. F. Heck. J. Org. Chem., 43, 2454, 1978; PA1 R. F. Heck, Acc. Chem. Res., 12, 146, 1979; PA1 R. F. Heck, Pure & Appl. Chem., 50, 691, 1978; PA1 B. A. Patel, J. E. Dickerson and R. F. Heck, J. Org. Chem., 43, 5018, 1978; PA1 T. C. Zebovitz and R. F. Heck, J. Org. Chem., 42, 3907, 1977; PA1 H. A. Dieck and R. F. Heck, J. Am. Chem. Soc., 96, 1133, 1974; PA1 J. B. Melpolder and R. F. Heck, J. Org. Chem., 41, 265, 1976; PA1 B. A. Patel and R. F. Heck, J. Org. Chem., 43, 3898, 1978; PA1 J. E. Plevyak, J. E. Dickerson, and R. F. Heck, J. Org. Chem., 44, 1979; PA1 R. Odle, B. Blevins, M. Ratcliff and L. S. Hegedus, J. Org. Chem., 45, 2709, 1980; PA1 I. Arai and G. D. Daves, Jr., J. Org. Chem., 44, 21, 1979; PA1 Y. Tamaru, Y. Yamada and Z.-I. Yoshida, J. Org. Chem., 43, 3396, 1978; and PA1 Y. Tamaru, Y. Yamada and Z.-I. Yoshida, Tet. Lett., 919, 1978. PA1 R. G. Miller, D. R. Fahey, H. Golden and L. C. Satek, J. Organomet. Chem., 82, 127, 1974; PA1 D. R. Fahey and J. E. Mahan, J. Molec. Catal., 3, 447, 1978; PA1 M. Mori and Y. Ban, Tet. Lett., 1803, 1976; PA1 M. Mori and Y. Ban, Tet. Lett., 1807, 1976; PA1 M. Mori, S. Kudo and Y. Ban, J. C. S. Perkin I, 771, 1979; and PA1 M. Mori and Y. Ban, Tet. Lett., 1133, 1979. PA1 (1) a nickel compound containing no radicals in which N and O are bonded directly together; PA1 (2) a triarylphosphine having 6 to about 14 carbons in each aryl moiety, and PA1 (3) zinc metal, at a temperature of about 25.degree. C. to about 250.degree. C.;
With nickel systems one has greater reactivity and the use of organic chlorides becomes possible, but up till now the reaction has only been demonstrated by intramolecular olefin arylation as shown in the publications listed below.